Method of dyeing keratinaceous materials with p-phenylene diamine compositions



United States Patent METHOD OF DYEING KERATINACEOUS MATE- RIALS WITHp-PHENYLENE DIAMINE COMPO- SITIONS Walter H. Brunner, Easton, Pa., andAlexander Halasz, Stamford, Conn. No Drawing. Filed Oct. 13, 1960, Ser.No. 62,321

. 11 Claims. (Cl. 16788) This invention relates to novel dyeingcompositions and methods for dyeing keratinaceous materials by the useof the novel compositions. This application is a continuation-in-part ofour (to-pending application Ser. No. 55,136, which was filed onSeptember 12, 1960.

The novel dyeing compositions of this invention contain as the colorforming agent or dyeing compound a p-phenylene diamine having thefollowing generic formula:

H-I I-H wherein R is a member selected from the group consisting of analkyl radical having from 1 to 4 carbon atoms, and the phenyl radical.Illustrative of a. specific compound represented by the aboveillustrated generic formula there can be mentioned:

HNH

(l) 2-nitro 4-amino N-methyl aniline In addition to the aboveillustrated compound there can also be mentioned: Z-nitro 4-aminoN-ethyl aniline; Z-nitro 4-amino N-propyl aniline; 2-nitro 4-arnino N-isopropyl aniline; Z-nitro 4-amino N-butyl aniline; 2-nitro 4-aminoN-phenyl aniline.

The p-phenylene diamines employed in this invention wherein thesecondary amino group is ortho to the nitro radical can be produced byfirst hydrogenating a 2,4- dinitrophenylamine wherein the amino groupcarries the phenyl or an alkyl radical e.g. N-methyl 2,4-dinitroaniline,by introducing hydrogen into a mixture of (a) a solution of the2,4-dinitrophenylarnine in an organic polar solvent such as ethanol; (b)a catalytically effective quantity of a platinum group metalhydrogenation catalyst such as platinum; and (c) a sutficient quantityof an aqueous solution of an acid to give the mixture a pH of less thanabout 4 wherein the said acid employed has a dissociation constantgreater than 1X10, such as sulfuric acid. About 3 moles of hydrogen arereacted per mole of the dinitro compound at a temperature of about 60 C.and a pressure of about 2 atmospheres. The hydrogenation produces theacid addition salt of the product 2-nitro 4- amino phenylamine. Torecover the 2-nitro 4-amino phenylamine free of the acid addition saltthe conventional techniques of neutralizing the acid to recover the freebase can be employed.

The p-phenylene diamines employed in the dyeing compositions of thisinvention are advantageously employed for dyeing keratinaoeous fibersand particularly human hair, e.g., living human hair, Without the use ofthe conventional peroxide additives, e.g. hydrogen peroxide, for colorformation or fixation to keratinaceous materials. There are known nitroderivatives of phenylene 3,088,877 Patented May 7, 1963 diamines whichthe prior art describes as agents for dyeing keratinaceous material. Theprior art teaches that various side chains or radicals such as hydroxylradicals are a necessary part of such phenylene diamines particularlywhen used without the aid of conventional peroxide oxidizing agents,e.g., hydrogen peroxide. However, it has now been discovered that thehydroxyl-free phenylene diamine derivatives of this invention haveexcellent dyeing properties when applied to keratinaceous material suchas human hair and that the excellent dyeing properties can be obtainedeven without the use of conventional peroxide oxidizing agents. Thenitro derivatives of the phenylene diamines employed in this inventionpossess many advantageous properties over other nitro derivatives ofphenylene diamines described by the prior art for dyeing keratinaceousmaterial, either with or without the use of conventional peroxideadditives. Such advantageous properties include a pronounced afiinityfor the hair and an actual penetration of the hair shaft; 21 good dyeingunion with both normal and permanently waved hair, particularly grayhair; an improved dyetake which is deep and uniform; good rubfastness;an improved washfastness, e.g. upon sh'arnpooing; production of brightand lustrous shades over a wide color range; freedom from staining thescalp; or good stability and dyetake over a wide pH range, including thepH range of about 7.5 to about 9.5 whereas many prior art compoundsrequire pH values above 9.5, such as a pH of 10 or higher forsatisfactory stability and dyetake.

The novel dyeing compositions of this invention comprise an aqueousalkaline solution of the specified phenylene diamines. In adition to thewater, alkalizing agent and phenylene diamine compound, the compositionscan also contain the conventional ingredients found in dyeingcompositions such as organic solvents for the dye, thickeners,detergents, gums, and the like. The compositions can be applied tokeratinaceous materials by the conventional techniques used in the art.Illustratively, when applied to living hair on the human head thecompositions can be applied to the hair with a brush, sponge, or othermeans of contact, such as dipping until the hair is properly saturatedWith the composition. The reaction time or time of contact of the dyeingcomposition with the keratinaceous material is not critical and can varyover the wide range used in the dyeing art such as periods of about 5minutes to about 2 hours and preferably from about minutes to about 60minutes. The dyeing temperature can vary over wide limits as isconventional in the art. Thus, the dyeing temperatures can vary fromabout room temperature, e.g., about C. to above about 60 C. andpreferably from about 20 C. to about C.

The dyeing compositions of this invention can be prepared by theconventional methods used in the dyeing art. Thus, they can be preparedby dissolving or dispersing the dye in water of the desiredconcentration. Water miscible organic solvents can be employed tofacilitate solution of the dye; in this event, the dye can be dissolvedfirst in the solvent and then diluted with water. Illustrative of theorganic solvents which can be used, there can be mentioned: alkylmonohydric alcohols such as those having from 1 to 6 carbon atoms, e.g.,ethanol, isopropanol, ctc.; alkyl dihydric alcohols such as those havingfrom 2 to 6 carbon atoms e.g. propyleneglycol', and various polyhydricalcohols, ketones or esters. The dispersion of the various ingredientscan also be facilitated by addition of a detergent or dispersing agentsuch as lauryl or myristyl sulfate or sulfonate.

Any water-soluble alkalizing agent that will not interfere (i.e., iscompatible) with the dye employed, and will not precipitate the dye orintroduce any possibility of toxicity under the conditions of use, orinjure the scalp or hide of the pelt, at its ultimate concentration inthe composition to be applied to the keratinaceous material, can beused. A preliminary test of some selected alkalizing agent can be madeto note its compatibility with the dye or to introduce possibility oftoxicity or injury.

Ammonium hydroxide, because of its freedom from toxicity over a wideconcentration range and its economy is an acceptable alkalizing agent.However, there can be used in place of, or together with the ammonia,any other compatible ammonia derivative alkalizing agent such as a loweralkylolamine such as mono-, di-, or triethanolamine, or a heterocyclicamine as morpholine, or a lower alkyl monoor diamine such asmonomethylamine, dimethylamine, monoethylamine, or diethylamine oramines such as tetraethylenepentamine, propylenediamine,dipropylenetriamine, etc. Any of these ammonia derivative alkalizingagents as well as ammonium hydroxide may be broadly referred to as anammonium alkalizant.

Also, as alkalizing agent, any alkaline earth hydroxide, for example,calcium hydroxide or magnesium hydroxide, can be used up to the limit ofits water-solubility and at any concentration that fails to produce aprecipitate with any of the components of the composition. The dissolvedalkaline earth hydroxide is preferred over the alkali metal hydroxides,such as sodium hydroxide, or potassium hydroxide, or carbonates, such assodium carbonate and bicarbonate, and of which can also be used so longas its ultimate concentration in the final dyeing solution is below thatwhich might possibly irritate the scalp, or injure the hide of the furpelt.

The quantity of the various ingredients in the dyeing compositions ofthis invention can vary over a wide range. The phenylene diaminecolorants of this invention can be employed in the conventionalconcentrations used in the dyeing of the various keratinaceousmaterials. Illustratively, tinctorially effective quantities of thephenylene diamine compound can vary from less than about .01% to greaterthan about 10% by weight of the aqueous solution. In the dyeing ofliving human hair the concentration of the dye will preferably vary fromabout 0.05% to about 5% by weight of the aqueous solution andparticularly from about 0.1% to about 3%. Any selected compatiblealkalizing agent should be used to give a pH greater than 7, such asabout 7.5 to about 12 and preferably from about 8 or 8.5 to 11. Thequantity of the alkalizing agent employed can vary over a wide rangedepending on the dye and particular alkalizing agent employed. Thus, thealkalizing agent can vary from about 0.1% to about 5% and preferablyfrom about 0.5% to about 2% by weight of the aqueous solution. The watercontent of the composition is ordinarily the major constituent and canvary over a wide range dependent in large measure on the quantity ofother additives such as solvents.

The phenylene diamines employed in this invention are water dispersablein the usual generic sense as embracing true solutions of the dyes inwater or any aqueous medium within the bounds of the invention as wellas stable homogeneous colloidal solutions of them in such aqueousmedium. Thus, the aqueous medium includes the aqueous alkaline medium.It includes also any aqueous medium containing, for example, asufficient amount of a compound, e.g., ethanol, employed as a commonsolvent to enhance the solution of the dye or some other organicmaterial. The composition can be formulated as solutions, gels,emulsions, dispersions, and the like.

The following examples are illustrative of the invention:

EXAMPLE 1 Reduction of N-Methyl 2,4-Dinirraniline to Z-Nitro 4-AminoN-Methyl Aniline In a hydrogenation apparatus there were charged 0.5gram of platinum on charcoal, a mixture of 9.9 grams of pulverizedN-methyl-Z,4-dinitroaniline in 200 ml. of

ethanol (95% ethanol content) and 20 ml. of concentrated (38%)hydrochloric acid. The reaction mixture was heated to 60 C. and held atthis temperature while there was introduced into the reaction chamber,with constant shaking, 0.303 gram (0.15 mole) of hydrogen at a pressureof to 40 p.s.i. (over a period of about 30 minutes). After cooling thereaction mixture to room temperature, a mixture of the catalyst and thehydrochloride of the nitroamine separated as yellow crystals. Thesecrystals were filtered off, dissolved in 50 ml. of hot water and theundissolved catalyst filtered off. The filtrate was cooled and theresulting acid addition salt of 2-nitro 4-amino N-methyl aniline whichprecipitated out of solution was recovered by filtration. This acidaddition salt was subsequently neutralized with ammonia to obtain thebasic form of the 2-nitro 4-amino N-methyl aniline which had a dark redcolor.

EXAMPLE 2 Reduction of N-Ethyl 2,4-Dinitroaniline to Z-Nitro 4-AminoN-Ethyl Aniline By following the process described in Example 1 therewas hydrogenated 22.0 grams (0.1 mole) of N-ethyl 2,4- dinitroaniline byhydrogenating with 0.605 gram of hydrogen (0.3 mole). From the resultinghydrochloride salt of Z-nitro 4-amino Nethyl aniline the free base wasprepared by neutralization with sodium carbonate. The free base form ofthe 2-nitro 4-amino N-ethyl aniline had a red color.

EXAMPLE 3 Reduction of N-Phenyl-2,4-Dinitr0aniline to Z-Nitro 4-Amin0N-Phenyl Aniline Into a hydrogenation apparatus there was charged 0.2gram of platinum on charcoal (5%), 2 ml. of water, 20 ml. ofisopropanol, 13.2 g. ,5 mole) N-phenyl 2,4-dinitroaniline, an additional80 ml. of isopropanol and 20 grams of a 50% aqueous solution of H 50 Thetemperature of the reaction mixture was brought up to about 65 C. andthen there was introduced into the reactor at a pressure of 50 to 40p.s.i. about .303 gram (0.15 mole) of hydrogen over a period of 17minutes. The temperature of the reaction mixture at the end of the 17minute period was 52 C. The reaction mixture was permitted to cool, theautoclave was opened and the sulfate salt of 2-nitro 4-amir1o N-phenylaniline which was produced by the hydrogenation was filtered off as aprecipitate. This sulfate salt was subsequently alkalized and separatedto obtain the 2-nitro 4-amino N-phenyl aniline as red crystals.

EXAMPLE 4 Reduction of N-Phenyl 2,4-Dinilr0aniline to Z-Nitro 4-AminoN-Phenyl Aniline Into a hydrogenation apparatus there was charged 0.5gram of a 5% platinum on charcoal catalyst, 10 ml. of concentratedhydrochloric acid (38% HO] content), 13 grams mole) of N-phenyl2,4-dinitroaniline in 200 ml. of ethanol. The reaction mixture washeated to a temperature of C. to C. and hydrogenated at 50 to 40 p.s.i.After the reaction mixture had absorbed 0.15 mole of hydrogen, thereaction mixture was cooled to room temperature and the reaction mixturewas filtered from the catalyst. To the filtrate was added 200 ml. ofwater and a large excess of sodium bicarbonate. The mixture waspermitted to stand for several hours whereupon the reaction product2-nitro 4-amino N-phenyl aniline crystallized out of solution and wassubsequently isolated by filtration.

EXAMPLE 5 A dyeing composition was prepared by dissolving 5 grams of2-nitro 4-amin0 N-methyl aniline in 50 grams of ethanol at 50 C. Theethanolic solution of the aniline compound was then added, withstirring, to a mixture containing 500 grams of water, grams ofdiethanolamine and 1 gram of agar agar as a thickener. The mixture wasthen heated to a temperature of about to 37 C. and applied to the hairby simply pouring the mixture over the hair. The dyeing mixture was lefton the hair for 20 minutes and then it was rinsed out with water. Thehair was dyed a beautiful dark red color without scalp staining.

EXAMPLE 6 There was substituted in the composition and process ofExample 5, Z-nitro 4-amino N-ethyl aniline instead of the Z-nitro4-amino N-methyl aniline. The hair was dyed a bluish-red shade.

EXAMPLE 7 The following dyeing composition was prepared. Ingredient:iiiiii c lil iifs fiiin (a) Carbopol 934 (a polycarboxylated vinyl resinmanufactured by the B. F. Goodrich Co.) 1.00 (1)) Sodium dodecyl benzenesulfonate 1.2 (c) Triethanolamine 0.5 (d) Water 91.2 (e) DispersedYellow No. 5 (Color Index designation) 0.25 (f) Z-nitro 4-amino N-ethylaniline 0.10 (g) Isopropanol 5.75

The composition of Example 7 was prepared by first forming a mixture ofingredients (a) to (d), inclusive, and finally adding to this mixture asolution of ingredients (e) to (g), inclusive. The dyeing compositionwas poured on human heads having gray hair and was permitted to remainon the hair for 20 minutes at room temperature before the hair wasrinsed with water. A blonde shade was obtained on the hair.

EXAMPLE 8 The following dyeing composition was prepared.

Percent by weight of composltlol (a) Acrylic acid Ingredient The dyeingcomposition of Example 8 was produced by first preparing a solution ofingredients (0) to (d), inclusive, and finally adding to this solution asolution of ingredients (e) to (i), inclusive. The dyeing compositionwas poured on to human heads having gray hair and permitted to remain onthe hair for about half an hour at room temperature, after which timethe hair was rinsed with water. The hair was dyed a brown shade.

What is claimed is:

l. A composition for dyeing keratinaceous material consistingessentially of an aqueous solution of from about 0.05% to about 5%, byweight, of a phenylene diamine having the following generic formula:

II-ITI-R wherein R is a member selected from the group consisting of analkyl radical having from 1 to 4 carbon atoms and the phenyl radical; ananionic detergent; and a sufficient quantity of an alkalizing agent togive the aqueous solution a pH of about 7.5 to about 12.

2. The composition of claim 1 wherein R of the generic formula is analkyl radical having from 1 to 4 carbon atoms.

3. A hair dyeing composition consisting essentially of an aqueoussolution containing from about 0.05 to about 5%, by weight, of aphenylene diamine having the generic formula:

H-N-II wherein R is a member selected from the group consisting of analkyl radical having from 1 to 4 carbon atoms and the phenyl radical; ananionic detergent; and a sufiicient quantity of an alkalizing agent toimpart a pH of about 8 to about 11 to the said aqueous solution.

4. The composition of claim 3 wherein the phenylene diamine compound is2-nitro 4-amino N-methyl aniline.

5. The composition of claim 3 wherein the phenylene diamine compound is2-nitro 4-amino N-ethyl aniline.

6. A process for dyeing keratinaceous material which comprises applyingthereto a tinctorially efiective quantity of an aqueous solutionconsisting essentially of a phenylene diamine compound having thefollowing generic formula:

generic formula:

H-N-R H-NII wherein R is a member selected from the group consisting ofan alkyl radical having from 1 to 4 carbon atoms and the phenyl radical;a sufficient quantity of an ammonium alkalizant to impart a pH of about8 to about 11 to said aqueous solution; and wherein the said aqueoussolution is at a temperature of about 20 C. to about 45 C.

8. The process of claim 7 wherein the phenylene diamine compound is2-nitro 4-amino N-methyl aniline.

9. The process of claim 7 wherein the phenylene diamine compound is2-nitro 4-amino N-othyl aniline.

10. A composition for dyeing keratinaceous material comprising anaqueous solution consisting essentially of about 0.05% to about 5% byweight of 2-nitro 4-amino N-phenyl aniline and a suflicient quantity ofan alkalizing agent to give the aqueous solution a pH of about 7.5 toabout 12.

11. A process for dyeing keratinaceous material which comprises applyingthereto a tinctorially effective quantity of an aqueous solutionconsisting essentially of Z-nitro 4-amino N-phenyl aniline and asuflicient quantity of an 8 alkalizing agent to impart a pH of fromabout 8 to about OTHER REFERENCES 11 to the Sald aqueous solunon'Venkataraman: The Chemistry of Synthetic Dyes, vol.

References Cited in the file of this patent 1, Academic Press Inc., N.Y.(1952), pp. 323-324.

UNITED STATES PATENT Heilingotter: Am. Perfumer and Essential OilReview,

S May 1954, pp. 345448. 1,900,454 Marx Mar. 7, 1933 2,692,288 Bell Oct.19, 1954

1. A COMPOSITION FOR DYEING DERATINACEOUS MATERIAL CONSISTINGESSENTIALLY OF AN AQUEOUS SOLUTION OF FROM ABOUT 0.05% TO ABOUT 5%, BYWEIGHT, OF A PHENYLENE DIAMINE HAVING THE FOLLOWING GENERIC FORMULA: